CN109293693A - A kind of novel dithieno Silole organic solar batteries acceptor material and its preparation method and application - Google Patents
A kind of novel dithieno Silole organic solar batteries acceptor material and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of novel dithieno Silole organic solar batteries acceptor materials and its preparation method and application, the dithieno Silole organic solar batteries acceptor material is the non-fullerene organic solar batteries acceptor material of linear type with A-D-A structure, general structure are as follows:Wherein m is natural number, and the value of m is 2 or 3；R1And R2The alkyl straight-chain or straight chain that are carbon atom quantity from 1 to 20；B1And B2To draw electronics sealing end.It is simple that novel dithieno Silole organic solar batteries acceptor material of the invention overcomes existing non-fullerene small molecule receptor material molecule structure, molecular weight is small, preparation method is simple, and synthesis material is cheap and easily-available, is conducive to organic solar batteries commercial applications early.
Description
Technical field
The invention belongs to solar cell material technical fields, and in particular to a kind of novel dithieno silicon Polymorphs two
Alkene organic solar batteries acceptor material and its preparation method and application.
Background technique
Solar-photovoltaic technology has obtained significant progress in the past few decades, is shown according to related data, with GaAs
For core thin-film solar cells efficiency up to 28.8%, close to its theoretical maximum 30%.At the same time, organic solar
The development of battery also in growing with each passing hour, efficiency since most less than 1%, develop to today 17.3%, but organic at present
Solar battery is in the primary stage of theoretical research and industrialized development, and the photoelectric conversion efficiency of device, stability is still
There is huge room for promotion.Organic solar batteries are to be generated using organic photoelectrical material as semiconductor layer by photovoltaic effect
Electric current.Its working principle is that: under illumination condition, organic semiconductor layer absorbs photon, forms exciton (electron-hole constraint
It is right), when exciton diffusion is to receptor contact surface, exciton is dissociated into free electron and freely sky under to the effect of acceptor level difference
Cave, free electron and hole are mobile to positive and negative anodes respectively, are collected to form electric current.Organic solar batteries have it is easy to process,
Material source is wide, the features such as flexible material is as substrate can be used.
Organic solar batteries can be divided into all-polymer organic solar electricity according to the difference for using active layer material
Pond, full small molecule organic solar batteries, polymeric donor-small molecule receptor organic solar batteries, small molecule donor-polymerization
Four class of object receptor organic solar batteries, wherein with polymeric donor-small molecule receptor organic solar batteries efficiency highest, grinding
Study carefully at most, single-unit efficiency is up to 14.4% (Zhang S, Qin Y, Zhu J, et al.Over 14%Efficiency in
Polymer Solar Cells Enabled by a Chlorinated Polymer Donor[J].Advanced
Materials, 2018,30 (20): e1800868.), lamination efficiency is up to 17.3% (Meng L, Zhang Y, Wan X, et
Al.Organic and solution-processed tandem solar cells with 17.3%efficiency
[J].Science,2018.)。
In recent years, the development of polymeric donor-small molecule receptor organic solar batteries is very rapid, but its main grinds
Study carefully in terms of concentrating on small molecule receptor, but up to the present efficient small molecule receptor material structure is more single, synthesis is more
Complexity, such as with five, simultaneously for core, electron group is haled in introducing for (IDT) and seven bithiophene condensed ring (IDTT).Although above-mentioned material light
Photoelectric transformation efficiency is higher, and but its structure is complex, molecular weight is larger, and synthesis process material requested is expensive, preparation is difficult, is unfavorable for quotient
Industry application.Therefore, develop that one kind has both easily preparation and efficient small molecule receptor material seems particularly necessary.
Summary of the invention
In view of this, primary and foremost purpose of the invention is to provide a kind of novel organic sun of dithieno Silole
Energy battery acceptor material, the dithieno Silole organic solar batteries acceptor material is simple with structure, divides
Son measures smaller and efficient advantage.
To achieve the above object, scheme of the present invention is as follows:
A kind of novel dithieno Silole organic solar batteries acceptor material, the dithieno sila
Cyclopentadiene organic solar batteries acceptor material be the non-fullerene organic solar batteries of linear type with A-D-A structure by
Body material, general structure are as follows:
Wherein m is natural number, and the value of m is 2 or 3；
R1And R2The alkyl straight-chain or straight chain that are carbon atom quantity from 1 to 20；
B1And B2To draw electronics sealing end, structure is selected from structure as follows:
Further, when m is 3, R1And R2It is C8H17, B1And B2It isWhen, the dithieno sila
Cyclopentadiene organic solar batteries acceptor material is A1, the structural formula of the A1 are as follows:
Further, when m is 2, R1And R2For C8H17, B1And B2ForWhen, the dithieno sila ring
Pentadiene organic solar batteries acceptor material is A2, the structural formula of the A2 are as follows:
The second object of the present invention is to provide a kind of novel dithieno Silole organic solar
The preparation method of battery acceptor material, this method are simply easily prepared, and synthesis material is cheap and easily-available, is conducive to organic solar batteries
Commercial applications early.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of novel dithieno Silole organic solar batteries acceptor material, it is described
Novel dithieno Silole organic solar batteries acceptor material is A1, the structural formula of the A1 are as follows:
The preparation method of the A1, includes the following steps:
Twoport round-bottomed flask is taken, anhydrous and oxygen-free is handled, and under nitrogen protection, sequentially adds compound 4, the fluoro- 3- (two of 5,6- bis-
Cyanomethylene) 1-Indanone, pyridine, chloroform makees solvent, heat, reaction overnight, TLC monitoring, after reaction, by reaction solution
It is transferred in separatory funnel, methylene chloride extraction, saturated common salt water washing organic phase, organic phase is dry with anhydrous sodium sulfate, dense
With chloroform eluant, eluent is made after contracting cross pillar obtain black-and-blue solid A1.
Preferably, before the compound 4,5,6- bis- fluoro- 3- (dicyano methylene) 1-Indanone, pyridine, haloform reaction
MM than be 0.1:0.3:2.5:373.
Further, the compound 4 the preparation method comprises the following steps:
1) synthesis of compound 1: taking twoport round-bottomed flask, anhydrous and oxygen-free processing, and N ' dinethylformamide makees solvent, according to
Secondary addition dithieno Silole, phosphorus oxychloride, are stirred at room temperature, and overnight, TLC monitoring is added after reaction for reaction
Diluted sodium hydroxide solution is quenched, and reaction solution is transferred in separatory funnel, be extracted with ethyl acetate, saturated common salt water washing it is organic
Phase, organic phase is dry with anhydrous sodium sulfate, and with petroleum ether after concentration: methylene chloride makees eluant, eluent and crosses column, obtains faint yellow oily
Compound 1；
2) synthesis of compound 2: taking twoport round-bottomed flask, and chloroform makees solvent, is added at 1,0 DEG C of compound and NBS is added, extensive
Multiple to being stirred at room temperature, overnight, TLC is monitored for reaction, after reaction, reaction solution is transferred in separatory funnel, methylene chloride extraction
It takes, saturated common salt water washing organic phase, organic phase is dry with anhydrous sodium sulfate, and with petroleum ether after concentration: methylene chloride elutes
Column is crossed in agent, obtains yellow oily compound 2；
3) synthesis of compound 3: taking twoport round-bottomed flask, anhydrous and oxygen-free processing, and anhydrous tetrahydro furan makees solvent, and nitrogen is protected
Shield is lower to be added dithieno Silole, and n-BuLi is added at -78 DEG C, stirs one hour at -78 DEG C, is then added three
Methyl chloride tin restores to being stirred at room temperature, and overnight, it is molten that potassium fluoride is added into reaction solution after reaction for TLC monitoring for reaction
Liquid quenching reaction, reaction solution is transferred in separatory funnel, methylene chloride extraction, saturated common salt water washing organic phase, organic phase
It is dry with anhydrous sodium sulfate, yellow oily compound 3 is obtained after reduced pressure.
4) twoport round-bottomed flask is taken, anhydrous and oxygen-free processing sequentially adds compound 2, compound 3, tetra-triphenylphosphine palladium, sets
It changes nitrogen 3 times, toluene is added under nitrogen protection, be heated to reaction solution reflux, reaction is stayed overnight, TLC is monitored, and after reaction, is stopped
It only heats, after reaction solution is cooled to room temperature, reaction solution is transferred in separatory funnel, is extracted with dichloromethane, saturated salt solution
Organic phase is washed, organic phase is dry with anhydrous sodium sulfate, and with petroleum ether after concentration: methylene chloride makees eluant, eluent and crosses column, obtains red
Color oily compound 4.
Preferably, dithieno Silole described in step 1), phosphorus oxychloride, DMF reaction before mM
Than for 10:10:388；Compound 1 described in step 2), NBS, chloroform reaction before mM than be 3:3:249；Step 3)
Described in dithieno Silole, n-BuLi, trimethyltin chloride, tetrahydrofuran reaction before a mM ratio be
1:2.2:2.4:494；Compound 2 described in step 4), compound 3, tetra-triphenylphosphine palladium, dry toluene reaction before mmoles
You are than being 2.1:0.95:0.1:376.
The third object of the present invention is to provide a kind of novel dithieno Silole organic solar batteries
The preparation method of acceptor material, this method is simple and easy, and raw material is cheap and easily-available.
To achieve the above object, the present invention uses following scheme:
A kind of preparation method of novel dithieno Silole organic solar batteries acceptor material, it is described
Novel dithieno Silole organic solar batteries acceptor material is A2, the structural formula of the A2 are as follows:
The preparation method of the A2, includes the following steps:
Twoport round-bottomed flask is taken, anhydrous and oxygen-free is handled, and under nitrogen protection, sequentially adds compound 6, the fluoro- 3- (two of 5,6- bis-
Cyanomethylene) 1-Indanone, pyridine, chloroform makees solvent, heat, reaction overnight, TLC monitoring, after reaction, by reaction solution
It is transferred in separatory funnel, methylene chloride extraction, saturated common salt water washing organic phase, organic phase is dry with anhydrous sodium sulfate, dense
With chloroform eluant, eluent is made after contracting cross pillar obtain black-and-blue solid A2.
Preferably, before the reaction of the compound 6,5,6- bis- fluoro- 3- (dicyano methylene) 1-Indanone, pyridine, chloroform
MM than be 0.1:0.3:2.5:373.
Further, the preparation method of the compound 6, includes the following steps:
Twoport round-bottomed flask is taken, anhydrous and oxygen-free is handled, and under nitrogen protection, sequentially adds PdCl2 (PhCN) 2, KF, DMSO is done
Solvent, heating, overnight, after reaction, reaction solution is cooled to room temperature for TLC monitoring for reaction, and reaction solution is transferred to cold night leakage
It in bucket, is extracted with dichloromethane, saturated common salt water washing organic phase, organic phase is dry with anhydrous sodium sulfate, after organic phase concentration
It is crossed pillar with petroleum ether: methylene chloride and is obtained orange oily compound 6.
Preferably, mM ratio before the reaction of the compound 2, PdCl2 (PhCN) 2, KF, DMSO is 3:0.09:6:
352。
The fourth object of the present invention is to provide the novel dithieno Silole of one kind described in one kind organic
The application of solar battery acceptor material.
To achieve the above object, the present invention uses following scheme:
The novel dithieno Silole organic solar batteries acceptor material of described one kind is being used to prepare
Application in terms of organic solar batteries.
The fifth object of the present invention is to provide a kind of organic solar batteries.
To achieve the above object, the present invention uses following scheme:
A kind of organic solar batteries, including donor material and acceptor material, the acceptor material are that described one kind is new
The dithieno Silole organic solar batteries acceptor material of type, the donor material are PBDB-T, the PBDB-
The structural formula of T are as follows:
The beneficial effects of the present invention are: 1) the present invention provides a kind of novel dithieno Silole organic too
Positive energy battery acceptor material, wherein dithieno Silole organic solar batteries acceptor material A1 and A2 are simple
Linear structure, molecular structure is simple, molecular weight is small, has good visible absorption range and absorption intensity；
2) using bromo-reaction object and tin reagent as reaction when preparing product using stille method compared with the prior art
Raw material, the method that the present invention uses direct oxidation coupling, so that the dithieno Silole organic solar batteries
The preparation method of acceptor material A1 and A2 are simple, and synthesis material is cheap and easily-available；
3) the dithieno Silole organic solar batteries acceptor material is applied to organic solar electricity
In the photovoltaic device of pond, make element manufacturing cost substantially on the basis of guaranteeing that device obtains good absorption range and absorption intensity
Degree reduces, and is conducive to organic solar batteries commercial applications early；
To sum up, a kind of novel dithieno Silole organic solar batteries acceptor material gram provided by the invention
Having taken existing non-fullerene small molecule receptor material molecule, structure is complicated, and molecular weight is larger, and preparation process is difficult, and synthesis material is high
It is expensive and the disadvantages of be unfavorable for commercial applications, it is ideal organic solar batteries acceptor material.
Detailed description of the invention
Fig. 1 is the synthetic route chart for the acceptor material A1 that embodiment 1 is prepared.
Fig. 2 is the synthetic route chart for the acceptor material A2 that embodiment 2 is prepared.
Fig. 3 be normalization of the acceptor material A1 that is prepared of embodiment 1 respectively under weak solution and filminess it is ultraviolet-
Visible absorption spectra figure.
Fig. 4 be normalization of the acceptor material A2 that is prepared of embodiment 2 respectively under weak solution and filminess it is ultraviolet-
Visible absorption spectra figure.
Fig. 5 is the electrochemistry cyclic voltammetry curve figure of two kinds of acceptor materials A1 and A2.
Fig. 6 is that structure is ITO/PEDOT:PSS/ polymer P BDB-T/ (A1/A2)/DPO/Ag polymer solar electricity
The current -voltage curve figure of pond photovoltaic device.
Specific embodiment
Illustrated embodiment is in order to which preferably the present invention will be described, but is not that the contents of the present invention are limited only to institute
For embodiment.So those skilled in the art according to foregoing invention content to embodiment carry out it is nonessential improvement and
Adjustment, still falls within protection scope of the present invention.
Petroleum ether used in the following embodiment, DMSO, methylene chloride, ethyl acetate, chloroform, toluene, sodium hydroxide, layer
Analysis silica gel is purchased from Chuan Dong Chemical Co., Ltd.；Anhydrous N,N-dimethylformamide, anhydrous tetrahydro furan, n-BuLi, four triphens
Base phosphine palladium, pyridine are purchased from the smooth Co., Ltd of Haitai；Dithieno Silole, bis- fluoro- 3- (dicyano methylene of 5,6-
Base) 1-Indanone is purchased from Jiangsu Ji A Biotechnology Co., Ltd.It need to be using solvent purification system except toluene in the above buying reagent
System carries out outside Non-aqueous processing, and other reagents directly use.
Embodiment 1
A kind of novel dithieno Silole organic solar batteries acceptor material has the straight of A-D-A structure
The non-fullerene organic solar batteries acceptor material of line style, general structure are as follows:
When m is 3, R1And R2For C8H17, B1And B2ForWhen, the dithieno Silole is organic
Solar battery acceptor material is A1, the structural formula of the A1 are as follows:
The preparation method of the A1 is following (preparation route is as shown in Figure 1):
1) synthesis of compound 1: taking twoport round-bottomed flask, anhydrous and oxygen-free processing, and N ' dinethylformamide makees solvent, according to
Secondary addition dithieno Silole, phosphorus oxychloride, are stirred at room temperature, and overnight, TLC monitoring is added after reaction for reaction
Diluted sodium hydroxide solution is quenched, and reaction solution is transferred in separatory funnel, be extracted with ethyl acetate, saturated common salt water washing it is organic
Phase, organic phase is dry with anhydrous sodium sulfate, and with petroleum ether after concentration: methylene chloride makees eluant, eluent and crosses column, obtains faint yellow oily
Compound 1, the dithieno Silole, phosphorus oxychloride, the proportion of N ' dinethylformamide are as follows: dithieno
10 parts by weight of Silole: 10 parts by weight of phosphorus oxychloride: 30 parts by volume of N ' dinethylformamide, yield 85%；
2) synthesis of compound 2: taking twoport round-bottomed flask, and chloroform makees solvent, is added at 1,0 DEG C of compound and NBS is added, extensive
Multiple to being stirred at room temperature, overnight, TLC is monitored for reaction, after reaction, reaction solution is transferred in separatory funnel, methylene chloride extraction
It takes, saturated common salt water washing organic phase, organic phase is dry with anhydrous sodium sulfate, and with petroleum ether after concentration: methylene chloride elutes
Column is crossed in agent, obtains yellow oily compound 2, the proportion of compound 1, NBS, chloroform are as follows: 13 parts by weight of compound: 3 weight of NBS
Part: chloroform parts by volume 20, yield 76%；
3) synthesis of compound 3: taking twoport round-bottomed flask, anhydrous and oxygen-free processing, and anhydrous tetrahydro furan makees solvent, and nitrogen is protected
Shield is lower to be added dithieno Silole, and n-BuLi is added at -78 DEG C, stirs one hour at -78 DEG C, is then added three
Methyl chloride tin restores to being stirred at room temperature, and overnight, it is molten that potassium fluoride is added into reaction solution after reaction for TLC monitoring for reaction
Liquid quenching reaction, reaction solution is transferred in separatory funnel, methylene chloride extraction, saturated common salt water washing organic phase, organic phase
It is dry with anhydrous sodium sulfate, yellow oily compound 3, the dithieno Silole, positive fourth are obtained after reduced pressure
The proportion of base lithium, trimethyltin chloride, tetrahydrofuran are as follows: 1 parts by weight of dithieno Silole: 2.2 weight of n-BuLi
Measure part: 2.4 parts by weight of trimethyltin chloride: 40 parts by volume of tetrahydrofuran, yield 95%；
4) synthesis of compound 4: taking twoport round-bottomed flask, anhydrous and oxygen-free processing, sequentially add compound 2, compound 3,
Tetra-triphenylphosphine palladium is replaced nitrogen 3 times, and toluene is added under nitrogen protection, is heated to reaction solution reflux, reaction is stayed overnight, TLC is supervised
It surveys, after reaction, stops heating, after reaction solution is cooled to room temperature, reaction solution is transferred in separatory funnel, uses methylene chloride
Extraction, saturated common salt water washing organic phase, organic phase is dry with anhydrous sodium sulfate, and with petroleum ether after concentration: methylene chloride is washed
Column is crossed in de- agent, obtains Red oil compound 4, the proportion of the compound 2, compound 3, tetra-triphenylphosphine palladium, dry toluene
Are as follows: 2 2.1 parts by weight of compound: 30.95 parts by weight of compound: 0.1 parts by weight of tetra-triphenylphosphine palladium: 40 volume of dry toluene
Part, yield 82%；
5) synthesis of A1: taking twoport round-bottomed flask, and anhydrous and oxygen-free is handled, and under nitrogen protection, sequentially adds compound 4,5,
6- bis- fluoro- 3- (dicyano methylene) 1-Indanone, pyridine, chloroform make solvent, and 70 DEG C of heating, overnight, TLC monitoring is reacted for reaction
After, reaction solution is transferred in separatory funnel, methylene chloride extraction, saturated common salt water washing organic phase, organic phase nothing
Aqueous sodium persulfate is dry, with chloroform makees eluant, eluent after concentration and cross pillar obtaining black-and-blue solid A1, the compound 2, compound 3,
The proportion of tetra-triphenylphosphine palladium, dry toluene are as follows: 2 2.1 parts by weight of compound: 30.95 parts by weight of compound: four triphenylphosphines
0.1 parts by weight of palladium: 40 parts by volume of dry toluene, yield 72%.
Embodiment 2
A kind of novel dithieno Silole organic solar batteries acceptor material has the straight of A-D-A structure
The non-fullerene organic solar batteries acceptor material of line style, general structure are as follows:
When m is 2, R1And R2For C8H17, B1And B2ForWhen, the dithieno Silole is organic
Solar battery acceptor material is A2, the structural formula of the A2 are as follows:
The preparation method of the A2 is following (preparation route is as shown in Figure 2):
1) synthesis of compound 2 is as described in Example 1；
2) synthesis of compound 6: taking 100mL twoport round-bottomed flask, and anhydrous and oxygen-free is handled, and under nitrogen protection, sequentially adds
Compound 2 (3mmol), PdCl2 (PhCN) 2 (0.09mmol), KF (6mmol), DMSO (25mL) make solvent, are heated to 60 DEG C,
Overnight, TLC monitoring closes heating after reaction for reaction, and after reaction solution is cooled to room temperature, reaction solution is transferred to liquid separation leakage
It in bucket, is extracted with dichloromethane, saturated salt solution (100mL × 3) washing organic phase, it is dense after organic phase anhydrous sodium sulfate drying
Contracting, crosses column with chloroform and obtains orange oily compound 6, yield 60%；
3) synthesis of A2: taking 100mL twoport round-bottomed flask, and anhydrous and oxygen-free is handled, and under nitrogen protection, sequentially adds compound
6 (0.1mmol), 5,6- bis- fluoro- 3- (dicyano methylene) 1-Indanone (0.3mmol), pyridine (0.2mL), chloroform (30mL) are made
Solvent, 70 DEG C of heating, overnight, TLC monitoring is closed heating, after reaction solution is cooled to room temperature, will be reacted after reaction for reaction
Liquid is transferred in separatory funnel, and methylene chloride extraction, saturated salt solution (100mL × 3) washs organic phase, the anhydrous sulphur of organic phase
It is concentrated after sour sodium is dry, makees eluant, eluent with chloroform and cross column obtaining black-and-blue solid A2, yield 70%.
Embodiment 3
The optical property of novel dithieno Silole organic solar batteries the acceptor material A1 and A2
With chemical property parameter study.
The optical property and chemical property parameter study of A1 and A2 is as shown in table 1, and the electrochemical properties of A1 and A2 pass through
Cyclic voltammetry (CV) characterization.Ferrocene/ferrocene (Fc/Fc+) redox couple (being lower than vacuum level 4.8eV) is for calibrating
As interior target current potential.As shown in figure 5, being calculated from initial oxidation and reduction potential, the highest occupied molecular orbital (HOMO) of A1
It is -5.29eV and -3.93eV with lowest unoccupied molecular orbital (LUMO) energy level, A2 is respectively -5.26eV and -3.87eV.Fig. 3 and
Fig. 4 is respectively the normalization UV-visible absorption spectrum of acceptor material A1 and A2 respectively under weak solution and filminess, from
It can be seen that, wavelength locating for the maximum absorption band of long wave strong point is 858nm, phase under acceptor material A1 filminess in Fig. 3 and Fig. 4
786nm under being absorbed than solution, red shift 72nm；Wave locating for the maximum absorption band of long wave strong point under acceptor material A2 filminess
A length of 841nm, the 776nm under being absorbed compared to solution, red shift 71nm.This illustrates that acceptor material A1 and A2 are equal in the solid state
There is relatively stronger intermolecular interaction, causes π-π stacking under small molecule coherent condition closer orderly.
The optical property and chemical property parameter of table 1.A1 and A2
| Acceptor material | λSolution(nm) | λFilm(nm) | Egap opt(eV) | Eox onset(V) | HOMO(eV) | LUMO(eV) |
| A1 | 786 | 858 | 1.3 | 1.36 | -5.29 | -3.93 |
| A2 | 776 | 847 | 1.31 | 1.39 | -5.26 | -3.87 |
Embodiment 4
Use PBDB-T for donor material, A1 or A2 are acceptor material, according to ITO/PEDOT:PSS/PBDB-T:(A1/
A2 the performance study for the solar battery that)/B-n/DPO/Ag is fabricated to.
The polymer P BDB-T battery table with two kinds of acceptor material B-n respectively in the active layer of solar cell photovoltaic device
It is as shown in table 2 to reveal the photovoltaic performance parameter come, it is ITO/PEDOT:PSS/PBDB-T:(A1/ that table 2, which is listed based on structure,
A2 open-circuit voltage, short circuit current, fill factor and the photoelectricity of)/B-n/DPO/Ag polymer solar battery photovoltaic device turn
Change the main photovoltaic performance parameter such as efficiency；Current -voltage curve figure such as Fig. 6 institute of its polymer solar battery photovoltaic device
Show, when using A1 as acceptor material, the short circuit current and open-circuit voltage of device are respectively 21.4mA/cm2 and 0.64V；With A2 be by
When body material, the short circuit current and open-circuit voltage of device are respectively 20.5mA/cm2 and 0.7V.
The photovoltaic performance parameter of 2. solar battery of table
| Active layer | Jsc[mA/cm2] | Voc[V] | FF [%] | PCE [%] |
| A1 | 21.4 | 0.64 | 68 | 9.3 |
| A2 | 20.5 | 0.7 | 70.2 | 9.62 |
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (13)
1. a kind of novel dithieno Silole organic solar batteries acceptor material, which is characterized in that described two
Thieno Silole organic solar batteries acceptor material is that the non-fullerene of linear type with A-D-A structure is organic too
Positive energy battery acceptor material, general structure are as follows:
Wherein m is natural number, and the value of m is 2 or 3；
R1And R2The alkyl straight-chain or straight chain that are carbon atom quantity from 1 to 20；
B1And B2To draw electronics sealing end, structure is selected from structure as follows:
2. the novel dithieno Silole organic solar batteries receptor material of one kind according to claim 1
Material, which is characterized in that when m is 3, R1And R2It is C8H17, B1And B2It isWhen, the dithieno sila ring
Pentadiene organic solar batteries acceptor material is A1, the structural formula of the A1 are as follows:
3. the novel dithieno Silole organic solar batteries receptor material of one kind according to claim 1
Material, which is characterized in that when m is 2, R1And R2It is C8H17, B1And B2It isWhen, the dithieno sila ring
Pentadiene organic solar batteries acceptor material is A2, the structural formula of the A2 are as follows:
4. a kind of preparation method of novel dithieno Silole organic solar batteries acceptor material, feature exist
In the novel dithieno Silole organic solar batteries acceptor material is A1, the structural formula of the A1
Are as follows:
The preparation method of the A1, includes the following steps:
Pyridine is sequentially added in compound 4 and 5,6- bis- fluoro- 3- (dicyano methylene) 1-Indanone, chloroform heat instead
It answers, is extracted through methylene chloride, obtain A1 after chloroform elutes after washing, dry, being concentrated.
5. the preparation method according to claim 4, which is characterized in that (dicyano is sub- by the compound 4, the fluoro- 3- of 5,6- bis-
Methyl) 1-Indanone, pyridine, before haloform reaction mM than being 0.1:0.3:2.5:373.
6. the preparation method according to claim 4, which is characterized in that the compound 4 the preparation method comprises the following steps:
1) dithieno Silole, phosphorus oxychloride the synthesis of compound 1: are sequentially added in N ' dinethylformamide
Reaction is stirred at room temperature, is extracted through methylene chloride, obtains compound 1 after washing, dry, being concentrated after dichloromethane eluent；
2) synthesis of compound 2: being added described in step 1) in chloroform and NBS be added at 1,0 DEG C of compound, is stirred at room temperature anti-
It answers, is extracted through methylene chloride, obtain compound 2 after washing, dry, being concentrated after dichloromethane eluent；
3) synthesis of compound 3: dithieno Silole being added in tetrahydrofuran, n-BuLi is added at -78 DEG C,
Stirring, adds trimethyltin chloride, and reaction is stirred at room temperature, and perfluorinated potassium is quenched, methylene chloride extraction, washing, drying, is concentrated
After obtain compound 3；
4) synthesis of compound 4: toluene is added in the compound 2 and 3, tetra-triphenylphosphine palladium and carries out heating reaction, through two
Compound 4 is obtained after dichloromethane eluent after chloromethanes extraction, washing, dry, concentration.
7. preparation method according to claim 6, which is characterized in that the Polymorphs of dithieno silicon described in step 1) two
Alkene, phosphorus oxychloride, DMF reaction before mM than be 10:10:388；Compound 1 described in step 2), NBS, chloroform it is anti-
A mM ratio before answering is 3:3:249；Dithieno Silole described in step 3), n-BuLi, trimethyl ammonia chloride
Tin, tetrahydrofuran reaction before mM than be 1:2.2:2.4:494；Compound 2 described in step 4), compound 3,43
Phenylphosphine palladium, dry toluene reaction before mM than be 2.1:0.95:0.1:376.
8. a kind of preparation method of novel dithieno Silole organic solar batteries acceptor material, feature exist
In the novel dithieno Silole organic solar batteries acceptor material is A2, the structural formula of the A2
Are as follows:
The preparation method of the A2, includes the following steps:
Pyridine and chloroform will successively be added in compound 6,5,6- bis- fluoro- 3- (dicyano methylene) 1-Indanone, heating is anti-
It answers, affords A2 through chloroform after methylene chloride extraction, washing, dry, concentration.
9. preparation method according to claim 8, which is characterized in that (dicyano is sub- by the compound 6, the fluoro- 3- of 5,6- bis-
Methyl) 1-Indanone, pyridine, chloroform reaction before mM than be 0.1:0.3:2.5:373.
10. preparation method according to claim 8, which is characterized in that the preparation method of the compound 6, including it is as follows
Step:
Compound 2, PdCl2 (PhCN) 2, KF are sequentially added, DMSO carries out heating reaction, through methylene chloride extraction, washing, does
The compound 6 is obtained through dichloromethane eluent after dry, concentration.
11. preparation method according to claim 10, which is characterized in that the compound 2, PdCl2 (PhCN) 2, KF,
A mM ratio before the reaction of DMSO is 3:0.09:6:352.
12. the novel dithieno Silole organic solar batteries of one kind described in claim 1-3 any one
Application of the acceptor material in terms of being used to prepare organic solar batteries.
13. a kind of organic solar batteries, including donor material and acceptor material, which is characterized in that the acceptor material is institute
The novel dithieno Silole organic solar batteries acceptor material of the one kind stated, the donor material are PBDB-
T, the structural formula of the PBDB-T are as follows:
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| CN111423464A (en) * | 2020-04-08 | 2020-07-17 | 华南理工大学 | Siloxane-based substituted aromatic condensed ring and preparation method and application thereof |
| JP2021022693A (en) * | 2019-07-30 | 2021-02-18 | 三菱ケミカル株式会社 | Organic semiconductor device and compound used therefor |
| JP2021034449A (en) * | 2019-08-20 | 2021-03-01 | 三菱ケミカル株式会社 | Organic semiconductor device and compound used therefor |
| CN113512053A (en) * | 2021-04-19 | 2021-10-19 | 中国科学院重庆绿色智能技术研究院 | Preparation method and application of multi-condensed-ring n-type semiconductor material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2021022693A (en) * | 2019-07-30 | 2021-02-18 | 三菱ケミカル株式会社 | Organic semiconductor device and compound used therefor |
| JP2021034449A (en) * | 2019-08-20 | 2021-03-01 | 三菱ケミカル株式会社 | Organic semiconductor device and compound used therefor |
| CN111423464A (en) * | 2020-04-08 | 2020-07-17 | 华南理工大学 | Siloxane-based substituted aromatic condensed ring and preparation method and application thereof |
| CN113512053A (en) * | 2021-04-19 | 2021-10-19 | 中国科学院重庆绿色智能技术研究院 | Preparation method and application of multi-condensed-ring n-type semiconductor material |
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